Color photograph or film and method of producing same



A Patented Dec. 18,1928;

UNITED STATES- PATENT OFFICE.

FREDERIG E. IVES, OF PHILADELPHIA, PENNSYLVANIA, ASSIGNCR TO CARL W.

FENNINGER, F PHILADELPHIA, PENNSYLVANIA.

COLOR PHOTOGRAPH on FILM AND MET OD or raonuomesaris.

No Drawing.

This invention relates to color photographs or films and to a method oi producing the same and particularly to a method of producing a multicolor picture or print or film wherein a plurality of differently colored images are successivelyproduced in the same colloid layer and to the product and intermediate products of such" a method. 10 A broad object-of the invention is to provide a multicolor picture or. print or film and to produce intermediate products useful in the production thereof and'to provide a simplified, efi'ective and improved method for producing such a' film or picture and color, are eliminated or substantially mini-' .mized. A particular object is also to provide a colloid layer that contains'a'colored image produced from a photographically -pfoduced image and within which layer a second image may be effectively and clearly produced photographically without delay or.

extensive preparatory treatment subsequent I to the production of the first image. In the practice of my invention either the two-color system or the three-color system may be used and since'the two-color system is considerably more simple and is satisfactory for generalpractical purposes my invention will be described in connection with the two-color system for purposes of illustration and elucidation butwith the understanding that it is not, limited thereto.

In the practice of my invention two or more simultaneously exposed views or series of views, respectively representing different colors are taken, preferably from substantially a Single view point, for the purpose of securing color selection negatives that are used in producing different colored positive- Application filed October 20, 1926. Serial No. 143,023.

images in the finalpicture, printer film. Such negatives that respectively represent different colorsmay be produced by. using interposed color screens orfilters or otherwise, as by theuse of dichroic reflectors, each such negative preferably being made with film that is especially sensitive. with respect to the colors recorded thereon.

; 'Aftersuch color representing negatives, for example a red-representing negative and a0 a green-representing negative, have been made, the sensitive colloid layer of the final print or picture or film is exposed tolight passing through one of the negatives, and development by ordinary means will pro- 05 duce a silver image from which an image of'one color is produced. Then the silver salt produced in the formation of that colored image 'is converted into a sensitive silver compound and the sensitive colloid layer is exposed to light through the negative that represents another color and again developed, and from the silver image so produced an image possessing another color..' is produced in the colloid layer. An addi- .75 tional image of still another color may be similarly produced and appear in the final print, picture or film;

' A plurality of images of different colors may be produced fromseparate appropriate negatives in the same surface and level of the sensitive colloid layer of the positive film or picture, or one image may be produced in one surface of the colloid layer and 1 another image may be produced from a reversed negative in the opposite surface thereof. It a plurality of images is producd in the inner surface of the colloid layer the negatives should not be reversed with respect to one another but they should be reversed with respect to 'originalnegatives that are not made through the carrier of the colloid if the final print-or picture is not to be reversed with respect to the subject photographed. Prints or films containing images of different colors in the same, colloid layer and produced from separatesilver images successively produced from salts of the same silver, and methods of producingsuch prints or films are disclosed in my Patents .No.

1,499,930 of July 1st, 1924 and No. 1,538,816

of May 19th, 1925, and other prints or films containing different colored images in' the same colloid la er and methods of producing them are escribed in my Patents No. 1,175,540 of February 8th, 1916 and No. 1,278,668 of September 10th, 1918, and the rints and processes of producing them which are there described are entirely useful and successful and the Present invention constitutes a still further improvement on those films or prints whereby those processes are improved and rendered more rapid and certain and the products are superior. The reversal of negatives in connection with printing on opposite or inner surfaces of a colloid layer is described in the aforementioned Patent No. 1,538,816

positive containing a silver image successively in the followlng baths:

Solution A. Water 460 c. c. OXalic acid 3. 24 grams.

Potassium ferricyanide 1 gram. Ferric chlorid solution,

U. S. P 16 c c The entire operation last referred to can be performed in one step by treating the developed and Washed, but unfixed, positive in the following bath:

and'in my Patent No. 1,320,760 of November Solution 4th, 1919. 4 W e n. 20 litres.

In practice the order in which different OXahq a 85 grams.

colored positive images are produced suc- POtaSSPIm ferrlqyamde gramscessively may be varied and variation may a siu 'q de 42grams.

be made in the location of such images in s lum ch10r1de 57 grams.

the same or different surfaces Or opposite surfaces of the colloid layer. In the best practice of my invention, however, the inner surface of the colloidlayer is first exposed to light Passing through a reversed p stated proportions in a manner well known resenting negative and through the carrier of the colloid layer. The exposed colloid layer is then developed by ordinary means, such as the well known monomethylparamidophenol sulfate (metol) developer, such developer preferably being dilute and without bromide'and the time of development being limited to the end that the ima e be thin and delicate although fully printed. The print will then comprise a colloid layer containing a silver image and a silver halide such as silver bromide. The silver image is then utilized for the formation of a blue image and the silver salt (silver ferrocyanide) produced from the silver of the silver image in the production of the blue image from that silver image, is converted into silver bromide with the result that the carrier thereafter contains a pigment blue ima e and its original silver bromide content of uniform depth and distribution. These operations may be carried out in two steps or in a single step. The operation of formin a blue image from a silver image in a colloid layer that also contains some of the original silver halide and then converting into silver bromide the salt produced from the silver of the silver image in the formation of the blue image, and thereby producing a colloid layer containing a blue image and a uniform layer of silver bromide, may be accomplished in 4 two steps by procedure in accordance with my Patent No. 1,588,816 above mentioned.

' This operation may be performed by treating the developed and washed, but unfixed,

U. S. P. ferric chloride solution; 43 c. c.

The duration of the time of immersion in this solution and the character of the image may be cont olled by varying the abovein the art. I

Regardless of whether the operation of blue toning the silver image and then bringing all the silver in the colloid layer into the form of silver bromide is performed in one or two steps, these operations are to be understood as an operation consisting of blue toning in conjunction with a bromide. Regardless of whether the operation is performed in one or two steps the blue toning forms a blue image corresponding to the silver image and the silver of the silver image is converted into silver ferrocyanide which is then converted by the bromide into silver bromide.

The blue toning process greatly and injuriously reduces the sensitiveness of silver bromide and the sensitiveness of the silver bromide. may berestored by treatment with a bath containing an oxidizing agent and a bromide, salt, provided treatment in that bath is followed by very thorough and prolonged washing. Such long continued washing consumes much valuable time and if it is uneven it produces an unevenness in any print subsequently made in the colloid layer containing the silver bromide.

The processes described in my Patents No. 1,499,930 and No. 1,538,816 and above described are entirely operative but even though the print is blue toned in conjunction with a bromide prolonged washing has been necessary to nullify the influences harmful to the sensitiveness of silver bromide that are created in the blue toning operation.

Attempts to neutralize-or eliminate these influences have ,proved not only inefficient-but injurious to the blue image.

I have discovered thatall undesirable conditions or effects of blue toning upon the sensitiveness of the silver bromide in a colloid layer containing a colored image, produced as above described, canbe neutralized or eliminated or overcome by treating such a colloid layer that has been subjected to blue toning treatment in a bath of sodium sulphate. The harmful effects of blue toning are so perfectly overcome by treatment in a bath of sodium sulphate that the film may be dried without washing 'and the blue image will remain unimpaired and the sensitiveness of the silver bromide will be greator or at least equal to the sensitiveness thereof attained heretofore as a result of prolonged washing.

In practice, I prefer to effect simultaneously the production of -a pigment blue image from the silver image and the conversion of-the silver salt thereby produced from the silver of the silver image into silver bromide, as bythe use of solution C and as described in my Patent No. 1,499,930, followed by treatment with the sodium sulphate bath. Moreover the addition of a small amount of a bromide to the sodium sulphate bath is advantageous, though not necessary, because its use leaves in the film when dry .a desirable quantity of free. bromide, and

its use also reduces the time necessary in the toning bath. Thus the toning operation with solution C may be continued for only five minutes provided such treatment is followed by' treatment for five minutes in a sodium sulphate bath consisting of:

Solution D. WVater 20 litres. Sodium sulphate (Glauber salts) 450 grams. Potassium bromide 30 grams.

It is my belief, although I do not wish to be bound by the theory, that the sodium sulphate, which is neutral and does not pos sess alkalinity which is inimical to the blue.

image, nevertheless has the property of neutralizing any acidity and removing or rendering harmless substances formed or introduced in the blue toningoperationthat are injurious to sensitivity. I do not intend that my invention shall be limited to the use of sodium sulphate, that substance having been referred to for the purpose of describing a specific embodiment of my invention, be-

, cause it is obvious that other salts having similar basic properties, for example, ammonium sulphate or potassium sulphate, may be used instead of sodium sulphate so long as t-he-sensitiveness of the silver bromide is restored and the print containing the blue image is not subjected to injurious alkalinity.

After such treatment the film may be dried immediately and then consists of a colloid layer containing a pigment blue print in an even layer of uniformly light-sensitive silver bromide, such layer being freedof conditions or substances inimical to the sensitiveness of the silver bromide. Such intermediate product is ready forthe production of another image by exposure to light passing through the green-representing negative preferably into the outer surface of the colloid layer. Development is preferably carried out with acid diamidophenol developer to conserve the blue image which might be permanently reduced to some extent in strongly alkaline developer but which recovers substantially its original strength by mere washing when the abovenamed developer is used. This development need seldom exceed one minute with a normal developer and theaction of the developer may advanta eously be stopped by a bath containing a little acetic acid. Quick development followed by use of acetic acid avoids injury to the blue image which may disappear but is restored in the fixing and washing if the development-is not injuriously prolonged.

The formulae above given are susceptible of considerable modification but the formula given for solution C possesses thetadvantage that selective hardening-of the colloid layer containing the blue print is avoided and the silver bromide content is evenly distributed and in favorable condition for production of the second image. Trea ment with solution C leaves the silver bromide-somewhat less sensitive than it was originally/but sufficiently sensitive for practical purposes.

The conversion of the second silver image into an image of a color different from that of the first image may be carried out as described in my Patent No. 1,538,816 and my patents therein referred to.

From the foregoing it will appear that a multi-color print or cinematographic film and an intermediate product useful in the production thereof and also a method of producing such photograph or film have beendescribed, which embody the principles and attain the objects of the present invention. Matters ofprocedure, manipulation, ingredients, arrangement, combination and other features may be modified without (leparting from the spirit of.my invent-ion as defined in the appended claims.

What I claim and desire to secure by Letters Patent of the United States is:

1. In photographic. color print making,

the process of preparing'for the printing of' a secondimage a colloid layer containing a photographic silver image and silver bromide, which comprises converting the silver ingredients for producing the blue image, and then treating the .resultant product in a bath containing an alkali sulphate.

2. In photographic color print making,

the process of preparing for the printing of a'second image a colloid layer containing a photographic Sl-lVEI image and silver bromide, which comprises converting the silver image to silver bromide and a pigment blue bromide.

3. An intermediate product in color photography comprising, a colloid slayer containing a color image and with light-sensitive silver bromide evenly distributed throughout its body and with resultant products injurious to sensitiveness of the silver bromide in a neutral condition. I

4:. In photographic color print making, converting a silver image in a colloid layer, also containing silver bromide into a pigment blue image and silver bromide by blue toning in conjunction with a bromide, followed by treatment .with a bath containing a neutral salt of an alkali and capable of neutralizing resultant acidity.

5. In photographic color print making,

' converting a silver image in a colloid layer also containing silver bromide, into-a pigment blue image and silver bromide by blue toning in conjunction with a bromide, followed by treatment with a bath containing sodium sulphate.

6. In photographic color print making, converting a silver image in a colloid layer also containing silver bromide, into a pigment" blue image and silver bromide by blue toning inco'njunction with a bromide, followed by treatment with a bath containing sodium sulphate and a bromide.

7. In photographic 'multi-color print making, converting a silver image in a colloid layer containing residual silver bromide into a pigment blue image and silver bromide, by blue-toning in conjunction with treatment with a bromide and also in conjunction with vtreatment with an alkali sulphate.

8. In photographic multi-color print mak ing, converting a silver image in a colloidlayer containing residual silver bromide into a pigment blue image and silver bromide, by blue-toning in conjunction with treatment with a bromide and also in conjunction with treatment with an alkali sulphate, followed by the photographic production of the second image in the same colloid layer.

9. In photographic multi-color print making an intermediate product comprising a colloid layer containing a blue-toned image and an even layer of light sensltive silver bromide and also containing an alkali 11. In photographic multi-color print making, converting a silver image in a colloid layer containing residual silver bromide into a pigment blue image and silver bromide by blue-toning, and treating the resulting product with an alkali sulphate and with a bromide. 7

12. In photographic multi-color print making in which a silver image in a colloid layer is converted into .a blue image by blue-toning, the steps consisting in treating the resulting product with a bromide and with an alkali sulphate.

13. In photographic multi-color print making in which a silver image'in a colloid layer containing also silver'bromide is converted into a blue image and silver bromide by blue-toning and treatment with a bromide, the step consisting of eliminating the necessity of extensive washing of'the layer containing a blue image and silver bromide, in preparation for the photographic produetion therein" of asecond image, by neutralizing the conditions in the layer containing the blue image and silver bromide which are injurious to sensitiveness of the silver bromide and were produced in the steps whereby the silver image therein was converted to a blue image and silver bromide.

14. In photographic multi-color print making in which a silver image in a colloid layer containing also silver bromide is converted into a blue image and silver bromide by blue-toning and treatment with a bromide, the step of preparing the layer containing the blue image and silver bromide for the photographic production therein of a second image, by neutralizing the conditions in the layer which wereproduced in the preceding treatment thereof and are injurious to the sensitiveness of the silver bromide therein, followed by drying of the layer without extensive washing thereof.

15. In photographic multi-color print making, the process comprising exposing through a color representing negative a colloid layer containing sensitive silver bromide, then by development converting the colloid layer lnto a layer containing a silver image and silver bromide, then converting the silver image to a pigment blue image and silver bromide by blue-toning and treatment with a bromide, then neutralizing the conditions in the layer which were produced by the preceding steps and are injurious to the sensitiveness of the silver bromlde'therein,

and then drying the colloid layer.

mide, then by development converting the colloid layer into a layer containing a silver image and silver bromide, then converting the silver image to a pigment blue image and silver bromide by blue-toning and treatment with a bromide, 'thenneutralizing the com ditions in thelayer which were produced by the preceding steps and are injurious to the bromide by blue-toning and treatment with bromide, and neutralizing with a salt of air alkali the conditions in the layer containing the blue image and silver bromide which are injurious to sensitiveness of the silver bromide and which were produced in the steps whereby the silver image was converted into a blue image.

18. In photographic multi-color print making, converting a silver image into a colloid layer containing residual silver bromide into a pigment blue image and silver bromide" by blue-toning and treatment with bromide, and neutralizing with a neutral sulphate the conditions in the'layer containsensitiveness of the silver bromide therein, ing the blue image and silver bromide which then drying the colloid layer, followed by photographic production of a second image in the same colloid layer.

17 In photographic multi-color print making, converting a silver image in a colloid layer containing residual silver bro mide into a pigment blue image and silver CERTIFICATE or:

Pam no." 1, 695, 284.

FREDERIG E. IVES.

are injurious to sensitiveness of the silver bromide. and which were produced in the steps whereby the silver image was converted into a blue image.

In testimony whereof, I have signed my name to this specification.

FREDERIC E. IVES,

common Gra'ntedf'Deeemher 18, I928, to

It is hereby certified. that the assignee in the above mmbered patent was erroneously issued to "Carl W, Fenoinger", whereas said patent should have been issued to "Carl W. Feinninge'r,.'lmstee", as shown by the records of assignments .lli this n; and an the a ham; Patent should be read with this correction therein thatfthe some my conform to the record of the case in the Pat-- en't Office Signed-and sum an" lsthm of mm A. n. 1929.

(Seal) I a M. J. Moore, Acting Commissioner of Patents. 

